US9638284B2 - Wear-resistant chain pin - Google Patents
Wear-resistant chain pin Download PDFInfo
- Publication number
- US9638284B2 US9638284B2 US14/772,104 US201414772104A US9638284B2 US 9638284 B2 US9638284 B2 US 9638284B2 US 201414772104 A US201414772104 A US 201414772104A US 9638284 B2 US9638284 B2 US 9638284B2
- Authority
- US
- United States
- Prior art keywords
- pins
- layer
- carbide
- wear
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G15/00—Chain couplings, Shackles; Chain joints; Chain links; Chain bushes
- F16G15/12—Chain links
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
- C23C12/02—Diffusion in one step
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/72—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes more than one element being applied in one step
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G13/00—Chains
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G13/00—Chains
- F16G13/02—Driving-chains
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G13/00—Chains
- F16G13/02—Driving-chains
- F16G13/04—Toothed chains
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G13/00—Chains
- F16G13/02—Driving-chains
- F16G13/08—Driving-chains with links closely interposed on the joint pins
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G13/00—Chains
- F16G13/18—Chains having special overall characteristics
Definitions
- the present invention relates to a chain pin which has improved wear resistance even in an environment in which degraded oil is used.
- a large number of links are endlessly joined by way of pins in a power transmission chain such as a silent chain or a roller chain, or a primary drive chain, and the pins are worn as a result of the links rotating and sliding about said pins while the chain is running.
- Various methods have therefore been proposed in the prior art in order to improve the wear resistance of the pins.
- the pin material is subjected to a chromizing treatment, whereby a hardened layer comprising chromium carbide is formed on the surface of the pin material.
- a hardened layer comprising at least one carbide from among chromium, titanium, vanadium, and niobium is formed on the surface of a pin material.
- JP 2003-269550 A A means such as that described in JP 2003-269550 A has been proposed in which a carbide layer comprising vanadium carbide as the main component and a small amount of chromium carbide is formed on the outermost surface part of steel forming the parent material of a pin, and a boundary layer in which the vanadium carbide content sharply decreases and the chromium carbide content sharply increases is formed at the boundary region between the carbide layer and the parent material.
- a carbide layer comprising vanadium carbide, which has high surface pressure strength, as the main component on the outermost surface part of the parent material, surface peeling of the carbide layer is unlikely to occur even under a high surface pressure, so the wear resistance of the pin is improved.
- a chromium-rich layer comprising a relatively large amount of chromium carbide which has a high level of bonding (adhesion) with the parent material and vanadium carbide is formed at the boundary layer between the carbide layer and the parent material, and as a result peeling of the carbide layer from the parent material is unlikely to occur even under a high surface pressure, so the wear resistance of the pin is further improved.
- the present invention has been devised in view of the conventional situation outlined above, and the problem to be solved by the present invention lies in providing a chain pin whereof the wear resistance can be improved even in an environment in which degraded oil is used.
- tungsten carbide As a carbide having high hardness and high robustness against oxidation.
- a WC layer is expected to reduce pin wear from chemical attack or soot attack in the environment of usage inside a turbo engine or a direct-injection engine.
- tungsten itself generally has a high melting point, and does not readily form directly on the surface of steel.
- the present invention has been devised in view of this situation, and the chain pin according to the present invention is such that a carbide layer comprising chromium carbide is formed on the outermost surface part of the steel forming the parent material of the pin, and tungsten carbide is diffused in said carbide layer (see claim 1 ).
- tungsten carbide is formed in the carbide layer on the outermost surface part of the steel, which means that the high hardness of the steel surface can be maintained while high robustness against chemical attack and soot attack from degraded oil can be demonstrated by the tungsten carbide in the carbide layer; as a result the wear resistance can be improved.
- tungsten carbide is diffused in the carbide layer comprising chromium carbide, and as a result it is possible to incorporate tungsten carbide which does not readily form directly on the surface of steel into the chromium carbide layer with the chromium carbide serving as a binder.
- the thickness of the carbide layer is preferably at least 10 ⁇ m (see claim 2 ).
- a steel material forming the parent material of the pin is introduced into a vessel together with chromium, tungsten carbide and a halide catalyst, and stirring is performed inside the vessel under a temperature of 750-950° C. in order to form a diffusion coating on the steel material, whereby a chromium carbide layer in which tungsten carbide is diffused is formed on the outermost surface part of the steel material (see claim 3 ).
- the lower limit of the temperature range for the diffusion coating is set at 750° C. because it is difficult to form a chromium carbide (CrC) layer if the temperature is lower than this
- the upper limit of the temperature range is set at 950° C. because it has been experimentally confirmed that it is difficult to form a tungsten carbide (WC) layer if the temperature is higher than this.
- the halide serving as a catalyst is preferably iron chloride (see claim 4 ).
- a carbide layer comprising chromium carbide is formed on the outermost surface part of the steel forming the parent material of the pin and tungsten carbide is diffused in said carbide layer, and therefore the high hardness of the steel surface can be maintained, while high robustness against chemical attack and soot attack caused by degraded oil can be demonstrated by the tungsten carbide in the carbide layer; as a result the wear resistance can be improved.
- tungsten carbide is diffused in the carbide layer comprising chromium carbide, and as a result it is possible to incorporate tungsten carbide which does not readily form directly on the surface of steel into the chromium carbide layer with the chromium carbide serving as a binder.
- FIG. 1 A schematic diagram in plan view of a silent chain employing the pin according to an exemplary embodiment of the present invention.
- FIG. 2 A schematic diagram in front view of the silent chain ( FIG. 1 ).
- FIG. 3 A view in longitudinal section of a rotary retort which is the apparatus for producing a pin ( FIG. 1 ).
- FIG. 4 An end view in cross section of the rotary retort ( FIG. 3 ).
- FIG. 5 A microscope photograph of the pin ( FIG. 1 ) in transverse section.
- FIG. 6 A schematic diagram of a wear testing apparatus for the silent chain ( FIG. 1 ) together with the test conditions.
- FIG. 7 A graph showing the results of wear resistance testing performed using the wear resistance apparatus ( FIG. 6 ) together with the results for conventional articles.
- FIG. 8 A graph showing the amount of wear of links and pins after wear resistance testing (after 100 hours) and the amount of wear of a conventional article.
- FIG. 1-8 illustrate the chain pin according to an exemplary embodiment of the present invention.
- the example of a pin for a silent chain is described herein.
- a silent chain 1 is constructed by stacking a large number of link plates 2 each having a pair of tooth parts 21 and a pair of pinholes 22 in the thickness direction (the vertical direction in FIG. 1 , the direction perpendicular to the page in FIG. 2 ) and the lengthwise direction (the left-right direction in FIGS. 1 and 2 ), while also pivotably and endlessly linking the link plates 2 using linking pins 3 which are inserted into the pinholes 22 .
- Guide links 4 are provided on the outermost side of the link plates 2 , and the ends of the linking pins 3 are fixed inside pinholes 41 in the guide links 4 . It should be noted that what are known as low-rigidity guides in which a crotch part 42 is formed on the back surface side are used here as an example of guide links.
- the linking pins 3 are produced using a production apparatus such as that shown in FIG. 3 and FIG. 4 .
- a rotary vessel (rotary retort) 11 is rotatably provided inside a furnace 10 .
- Spindles 12 are provided at both ends of the rotary retort 11 , the spindles 12 running through openings 10 a formed in both side wall parts 10 A of the furnace 10 .
- Bushes 13 are provided in the openings 10 a , and the spindles 12 of the rotary retort 11 are rotatably supported by the bushes 13 and tightly sealed therewith.
- the spindles 12 are drive-linked to a drive motor which is not depicted.
- a plurality of radial protrusions 14 are provided inside the rotary retort 11 .
- the rotary retort 11 is rotated at a predetermined speed by means of the drive motor, while heating in the furnace 10 is maintained at a temperature of 750-950° C. (preferably about 890° C.).
- a large number of linking pins 3 made of carbon steel to be coated and a particle mixture 15 are introduced into the rotary retort 11 .
- the particle mixture 15 includes a penetrant comprising chromium (Cr) powder and tungsten carbide (WC) powder, and a halide (iron chloride FeCl 3 in this case) catalyst.
- An operating time of the order of 30 hours is preferred, but this operating time is adjusted in accordance with the thickness of the carbide layer to be formed on the surface of the pins.
- the particle mixture 15 is mixed and agitated together with the linking pins 3 by the radial protrusions 14 inside the rotary retort 11 , as shown in FIG. 4 , and as a result the outer periphery of the linking pins 3 is placed in a state of constant contact with the particle mixture 15 .
- the lower limit of the temperature range is set at 750° C. because it is difficult to form a chromium carbide (CrC) layer if the temperature is lower than this
- the upper limit of the temperature range is set at 950° C. because it has been experimentally confirmed that it is difficult to form a WC layer if the temperature is higher than this (a WC layer is no longer formed when the temperature exceeds 1000° C. in particular).
- FIG. 5 shows a microscope photograph in transverse section of the linking pin 3 produced in the manner described above.
- a hardened layer having a thickness of about 10 ⁇ m is formed on the surface of the parent material of the linking pin 3 .
- the region of the hardened layer which appears gray is the chromium carbide (CrC) layer, and the region which appears white is tungsten carbide (WC).
- CrC chromium carbide
- WC tungsten carbide
- a large number of tungsten carbide (WC) particles are diffused in the chromium carbide (CrC) layer.
- the layer of resin provided over the hardened layer is used to fix the cut sample of the linking pin 3 in order to capture the microscope photograph.
- the wear test was carried out using the wear testing apparatus shown in FIG. 6 , the schematic structure being shown together with the test conditions.
- the testing apparatus is constructed by fitting 23-tooth sprockets S 1 , S 2 to a drive shaft D 1 and a driven shaft D 2 disposed with a gap therebetween, and a silent chain C for testing is wound onto the sprockets S 1 , S 2 .
- the rotation speed of the drive shaft D 1 of the wear testing apparatus was 6500 rpm.
- the lubricating oil temperature was 100° C. and the amount of oil was 1.0 liters/minute. Furthermore, the lubricating oil which was used had a total base number (TBN) of 1.
- TBN total base number
- the total base number generally indicates the amount of acid and base contained in oil, and is used as a reference to indicate the acid neutralizing capacity and cleanliness of oil.
- FIGS. 7 and 8 The results of the wear test employing the abovementioned wear testing apparatus are shown in FIGS. 7 and 8 .
- conventional article a indicates the example of a silent chain employing nitride pins which have been subjected to nitriding
- conventional article b indicates the example of a silent chain employing VC pins which have been coated with a vanadium carbide (VC) layer.
- FIG. 8 shows a comparison of the amount of wear of the links L and pins P as separate entities in the inventive article, and the amount of wear of the links L and pins P as separate entities in conventional article b after an operating time of 100 hours.
- the amount of wear of the links L after an operating time of 100 hours was about 21% less in the inventive article than in conventional article b, and the amount of wear of the pins P in the inventive article was about one quarter that of the conventional article b, which is clearly a considerable reduction.
- a chromium carbide layer in which tungsten carbide (WC) particles are diffused in a chromium carbide (CrC) layer is formed on the surface of the steel forming the parent material of the linking pins 3 , so it is possible to reduce wear of the pins and therefore of the chain as a whole even in an environment in which degraded oil is used.
- a rotary vessel rotary retort
- a rocking-type or agitation-type vessel may equally be used as the vessel into which the pins and particle mixture are introduced, rather than a rotary vessel.
- the present invention is suitable for pins for linking adjacent links in power transmission chains such as silent chains or roller chains, and primary drive chains.
- Patent Document 1 JP 56-41370 A (see the claims)
- Patent Document 2 JP 10-169723 A (see paragraph [0022])
- Patent Document 3 JP 2003-269550 A (see FIGS. 8 and 9 )
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Articles (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013051306A JP6118144B2 (ja) | 2013-03-14 | 2013-03-14 | 耐摩耗性を有するチェーン用ピンの製造方法 |
JP2013-051306 | 2013-03-14 | ||
PCT/US2014/023837 WO2014159475A1 (en) | 2013-03-14 | 2014-03-12 | Wear-resistant chain pin |
Publications (2)
Publication Number | Publication Date |
---|---|
US20160003324A1 US20160003324A1 (en) | 2016-01-07 |
US9638284B2 true US9638284B2 (en) | 2017-05-02 |
Family
ID=51625175
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/772,104 Active US9638284B2 (en) | 2013-03-14 | 2014-03-12 | Wear-resistant chain pin |
Country Status (5)
Country | Link |
---|---|
US (1) | US9638284B2 (ja) |
EP (1) | EP2971852B1 (ja) |
JP (1) | JP6118144B2 (ja) |
CN (2) | CN108825723A (ja) |
WO (1) | WO2014159475A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020194412A1 (ja) * | 2019-03-22 | 2020-10-01 | 大同工業株式会社 | チェーン伝動装置 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS566939A (en) | 1979-06-25 | 1981-01-24 | Daido Kogyo Co Ltd | Manufacture of bearing member for chain |
US6068568A (en) | 1996-12-12 | 2000-05-30 | Tsubakimoto Chain Co. | Silent chain |
US20020031687A1 (en) | 2000-06-29 | 2002-03-14 | Yumin Wang | Carbide coated steel articles and method of making them |
US20020119852A1 (en) * | 2000-12-27 | 2002-08-29 | Naosumi Tada | Chain pin and method of manufacturing same |
US20030176252A1 (en) | 2002-03-12 | 2003-09-18 | Borgwarner Morse Tec Japan K. K. | Silent chain |
US20060269763A1 (en) * | 2005-05-31 | 2006-11-30 | Honda Motor Co. Ltd. | Steel parts having high wear and abrasion resistance and method for manufacturing the same |
US7695575B2 (en) * | 2003-06-03 | 2010-04-13 | Daido Kogyo Co., Ltd. | Pin for chain and method for manufacture thereof |
US20150211603A1 (en) * | 2012-08-03 | 2015-07-30 | Iwis Motorsysteme Gmbh & Co. Kg | Friction- and wear-reducing joint for a bush chain or roller chain |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60114566A (ja) * | 1983-11-24 | 1985-06-21 | Sumitomo Metal Ind Ltd | 薄付けクロマイズ処理鋼製品の製造方法 |
JP2979102B2 (ja) * | 1996-08-05 | 1999-11-15 | 株式会社ハードフェース ウエルド カンパニー | 摺動部品の製造方法 |
JP2002130384A (ja) * | 2000-10-20 | 2002-05-09 | Tsubakimoto Chain Co | ロッカーピン型のサイレントチェーン |
JP2002327804A (ja) * | 2001-04-27 | 2002-11-15 | Tsubakimoto Chain Co | 超耐摩耗チェーン |
JP3719971B2 (ja) * | 2001-11-06 | 2005-11-24 | 株式会社椿本チエイン | 耐摩耗性被覆物を被覆したサイレントチェーン |
JP4944644B2 (ja) * | 2007-03-12 | 2012-06-06 | 本田技研工業株式会社 | チェーン |
WO2008120401A1 (ja) * | 2007-03-29 | 2008-10-09 | Daido Kogyo Co., Ltd. | 耐摩耗性チェーン |
-
2013
- 2013-03-14 JP JP2013051306A patent/JP6118144B2/ja not_active Expired - Fee Related
-
2014
- 2014-03-12 WO PCT/US2014/023837 patent/WO2014159475A1/en active Application Filing
- 2014-03-12 CN CN201810744284.3A patent/CN108825723A/zh active Pending
- 2014-03-12 EP EP14773358.8A patent/EP2971852B1/en not_active Not-in-force
- 2014-03-12 CN CN201480011371.8A patent/CN105190092A/zh active Pending
- 2014-03-12 US US14/772,104 patent/US9638284B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS566939A (en) | 1979-06-25 | 1981-01-24 | Daido Kogyo Co Ltd | Manufacture of bearing member for chain |
US6068568A (en) | 1996-12-12 | 2000-05-30 | Tsubakimoto Chain Co. | Silent chain |
US20020031687A1 (en) | 2000-06-29 | 2002-03-14 | Yumin Wang | Carbide coated steel articles and method of making them |
US6582765B2 (en) * | 2000-06-29 | 2003-06-24 | Borgwarner, Inc. | Carbide coated steel articles and method of making them |
US20020119852A1 (en) * | 2000-12-27 | 2002-08-29 | Naosumi Tada | Chain pin and method of manufacturing same |
US20030176252A1 (en) | 2002-03-12 | 2003-09-18 | Borgwarner Morse Tec Japan K. K. | Silent chain |
US7695575B2 (en) * | 2003-06-03 | 2010-04-13 | Daido Kogyo Co., Ltd. | Pin for chain and method for manufacture thereof |
US20060269763A1 (en) * | 2005-05-31 | 2006-11-30 | Honda Motor Co. Ltd. | Steel parts having high wear and abrasion resistance and method for manufacturing the same |
US20150211603A1 (en) * | 2012-08-03 | 2015-07-30 | Iwis Motorsysteme Gmbh & Co. Kg | Friction- and wear-reducing joint for a bush chain or roller chain |
Non-Patent Citations (1)
Title |
---|
International Search Report and Written Opinion dated Jun. 25, 2014 ; International Application No. PCT/US2014/023837; 9 pages. |
Also Published As
Publication number | Publication date |
---|---|
JP6118144B2 (ja) | 2017-04-19 |
EP2971852B1 (en) | 2018-01-31 |
CN108825723A (zh) | 2018-11-16 |
CN105190092A (zh) | 2015-12-23 |
EP2971852A1 (en) | 2016-01-20 |
EP2971852A4 (en) | 2016-11-30 |
JP2014177667A (ja) | 2014-09-25 |
WO2014159475A1 (en) | 2014-10-02 |
US20160003324A1 (en) | 2016-01-07 |
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